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Fundamentals of
SI ble
Chemical Science

© 2009 by Taylor & Francis Group, LLC

K10124_C000.indd i 2/4/2009 8:41:58 PM


© 2009 by Taylor & Francis Group, LLC

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Fundamentals 01
SUSlai Ie
Chemical Science
Stanlev E. Manahan

~CRC Press
V Taylor &. Francis Group
Boca Raton London New York

eRe Press is an imprint of the


Taylor &: Francis Group, an Inform. business

© 2009 by Taylor & Francis Group, LLC

K10124_C000.indd iii 2/4/2009 8:41:59 PM


CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-2742
© 2009 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works


Version Date: 20110715

International Standard Book Number-13: 978-1-4398-8208-5 (eBook - PDF)

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© 2009 by Taylor & Francis Group, LLC


CONTENTS

PREFACE XIII
AUTHOR XV

1. INTRODUCTION TO CHEMISTRY AND


GREEN CHEMISTRY 1
1.1. IF WE DO NOT CHANGE DIRECTION 1
1.2. THE ESSENTIAL ROLE OF CHEMISTRY 2
1.3. ENVIRONMENTAL CHEMISTRY AND GREEN CHEMISTRY 3
1.4. A MINI-COURSE IN CHEMISTRY 5
1.5. THE BUILDING BLOCKS OF MATTER 5
Subatomic Particles and Atoms 5
Atoms and Elements 6
The Periodic Table 7
1.6. CHEMICAL BONDS AND COMPOUNDS 8
Chemical Compounds 9
Ionic Bonds 10
1
Summary of Chemical Compounds and the Chemical Bond 111
Molecular Mass 11
1
1.7. CHEMICAL REACTIONS AND EQUATIONS 12
1
1.8. NUMBERS IN CHEMISTRY: EXPONENTIAL NOTATION 112
Addition and Subtraction of Exponential Numbers 13
1
Multiplication and Division of Exponential Numbers 114
1.9..
1.9 SIGNIFICANT FIGURES AND UNCERTAINTIES IN NUMBERS 115
Significant Figures in Calculations 15
1
Rounding Numbers 17
1
Use of Three Significant Digits 117
1.10. MEASUREMENTS AND SYSTEMS OF MEASUREMENT 18
1
SI Units of Measurement 118
Multiples of Units 18
1
Metric and English Systems of Measurement 118
1.11. UNITS OF MASS 2
20
1.12. UNITS OF LENGTH 21
2
1.13. UNITS OF VOLUME 222

© 2009 by Taylor & Francis Group, LLC

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vi Contents

1.14. TEMPERATURE, HEAT, AND ENERGY 23


2
Temperature Scales 23
2
Melting Point and Boiling Point 26
2
Heat and Energy 27
2
1.15. PRESSURE 2
27
1.16. UNITS
UNITS AND THEIR USE IN CALCULATIONS 2
28
Unit Conversion Factors 228
CHAPTER SUMMARY 3
31
Answers to Chapter Summary 33
3
LITERATURE CITED 36
3
QUESTIONS
QUE STIONS AND PROBLEMS 37
3

2. MATTER AND MATERIALS 45


2.1. WHAT IS MATTER AND WHY DOES IT MATTER
FOR SUSTAINABILITY AND GREEN CHEMISTRY? 45
4
2.2. CLASSIFICATION OF MATTER 46
4
Some General Types of Matter 47
4
Mixtures and Pure Substances 48
4
Summary of the Classification of Matter 49
4
2.3. QUANTITY OF MATTER: THE MOLE 49
4
The Mole and Avogadro’s Number 50
5
2.4. PHYSICAL PROPERTIES OF MATTER 550
Density 51
5
Specific Gravity 5
52
Color 53
5
Electromagnetic Radiation and Green Chemistry 554
2.5. STATES OF MATTER 555
2.6. GASES 5
56
The Gas Laws 57
5
Gas Law Calculations 59
5
2.7. LIQUIDS AND SOLUTIONS 62
6
Evaporation and Condensation
Condensation of Liquids 6
62
Vapor Pressure 63
6
Solutions 663
2.8. SOLIDS 6
65
2.9. THERMAL PROPERTIES 66
Melting Point 66
6
Boiling Point 66
6
Specific Heat 66
6
Heat of Vaporization 68
6
Heat of Fusion 669
Phase Change Materials in Green Technology 69
6
2.10. SEPARATION AND CHARACTERIZATION OF MATTER 770
Distillation 70
7
Separation in Waste Treatment 71
7
2.11. THE GREEN CHEMISTRY OF MATTER 74
7
CHAPTER SUMMARY 75
7
QUESTIONS AND PROBLEMS 8
81

© 2009 by Taylor & Francis Group, LLC

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Contents vii

3. ATOMS AND ELEMENTS 87


3.1. ATOMS AND ELEMENTS 8
87
3.2. THE ATOMIC THEORY 87
8
Laws That Are Explained by Dalton’s Atomic Theory 87
8
Small Size of Atoms 89
8
Atomic Mass 90
9
3.3. SUBATOMIC PARTICLES 990
3.4. THE BASIC STRUCTURE OF THE ATOM 991
Atomic Number, Isotopes, and Mass Number of Isotopes 91
9
Electrons in Atoms 92
9
3.5. DEVELOPMENT OF THE PERIODIC TABLE 93
9
3.6. HYDROGEN,
HYDROGEN, THE SIMPLEST ATOM 93
9
Designation of Hydrogen in the Periodic Table 994
Showing Electrons in Hydrogen Atoms and Molecules 94
9
Properties of Elemental Hydrogen 94
Production and Uses of Elemental Hydrogen 995
3.7. HELIUM, THE FIRST ATOM WITH A FILLED ELECTRON SHELL 95
Occurrence and Uses of Helium 996
3.8. LITHIUM, THE FIRST ATOM WITH BOTH INNER
AND OUTER ELECTRONS 97
9
Uses of Lithium 97
9
Lithium, a Key Material in Green Technology 999
3.9. THE SECOND PERIOD, ELEMENTS 4–10 999
Beryllium, Atomic Number 4 99
Boron, Atomic Number 5 100
10
Carbon, Atomic Number 6 101
10
Nitrogen, Atomic Number 7 101
10
Oxygen, Atomic Number 8 102
10
Fluorine, Atomic Number 9 103
10
Neon, Atomic Number 10 103
10
3.10. ELEMENTS 11–20, AND BEYOND 104
10
The Elements B Beyond
eyond Calcium 10
106
3.11. A MORE DETAILED LOOK AT ATOMIC STRUCTURE 107
10
Electromagnetic Radiation 107
10
3.12. QUANTUM AND WAVE MECHANICAL MODELS OF
ELECTRONS IN ATOMS 108
10
The Wave Mechanical Model of Atomic Structure 109
09
Multielectron Atoms and Quantum Numbers 111
11
3.13. ENERGY LEVELS OF ATOMIC ORBITALS 113
1
Hund’s Rule of Maximum Multiplicity 1115
3.14. SHAPES OF ATOMIC ORBITALS 116
11
3.15. ELECTRON CONFIGURATION 11
117
3.16. ELECT
ELECTRONS
RONS IN THE FIRST 20 ELEMENTS 118
1
Electron Configuration of Hydrogen 118
1
Electron Configuration of Helium 119
11
Electron Configurations of Elements 2–20 11
119
Lithium 119
19
Valence Electrons 119
19

© 2009 by Taylor & Francis Group, LLC

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viii Contents

Beryllium 120
12
Filling the 2p
2 Orbitals 120
12
Filling the 3s,
3 , 3p,
3 , and 4s
4 Orbitals 121
1
3.17. ELECTRON CONFIGURATIONS AND THE PERIODIC TABLE 1122
CHAPTER SUMMARY 126
1
Answers to Chapter Summary 1128
QUESTIONS AND PROBLEMS 131
13

4. CHEMICAL BONDS, MOLECULES,


AND COMPOUNDS 139
4.1. CHEMICAL BONDS AND COMPOUND FORMATION 13
139
Chemical Bonds and Valence Electrons 14
140
4.2. CHEMICAL BONDING AND THE OCTET RULE 14
141
The Octet Rule for Some Diatomic Gases 141
14
The Octet Rule for Chemical Compounds 14
141
4.3. IONIC BONDING 14
142
Electron Configurations of Ions from a Single Atom 142
14
Sodium Chloride as an Ionic Compound 143
14
Energetics in Ionic Bonding 145
14
Energy of Ion Attraction 146
1
Lattice Energy 14
147
Ion Size 14
147
Formation of Some Example Ionic Compounds 149
14
4.4. FUNDAMENTALS OF COVALENT BONDING 150
15
Chemical Bonds and Energy 150
15
Covalent Bonding 15
150
4.5. COVALENT BONDS IN COMPOUNDS 152
15
4.6. SOME OTHER ASPECTS OF COVALENT BONDING 154
15
Multiple Bonds and Bond Order 154
15
Lengths and Strengths of Multiple Bonds 155
15
Electronegativity and Covalent Bonding 156
15
Sharing Electrons—Unequally 157
15
Coordinate Covalent Bonds 158
15
Compounds That Do Not Conform to the Octet Rule 159
15
Resonance Structures 160
16
4.7. CHEMICAL FORMULAS OF COMPOUNDS 16
161
What a Chemical Formula States 16
161
Percentage Composition from Chemical Formulas 16
162
Calculation of Chemical Formulas 16
163
Empirical Formula from Percentage Composition 164
16
4.8. THE NAMES OF CHEMICAL COMPOUNDS 16
167
Binary Molecular Compounds 167
16
Names of Ionic Compounds 168
16
4.9. ACIDS, BASES, AND SALTS 170
17
Acids 170
17
Bases 171
17
Salts 1171
CHAPTER SUMMARY 172
17
Answers to Chapter Summary 173
1
QUESTIONS AND PROBLEMS 175
1

© 2009 by Taylor & Francis Group, LLC

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Contents ix

5. CHEMICAL REACTIONS, EQUATIONS,


AND STOICHIOMETRY 181
5.1. THE SENTENCES OF CHEMISTRY 181
18
Chemical Reactions and Equations: The Sentences of the Chemical Language 18
181
Quantitative Calculations from Chemical Equations 182
18
5.2. THE INFORMATION IN A CHEMICAL EQUATION 18
182
Chemical Reactions 182
18
Expressing a Chemical Reaction as a Chemical Equation 182
18
Symbols Used in Chemical Equations 183
18
5.3. BALANCING CHEMICAL EQUATIONS 184
18
Balancing the Equation for the Reaction of Hydrogen Sulfide
with Sulfur Dioxide 18
184
Some Other Examples of Balancing Equations 185
18
Summary of Steps in Balancing an Equation 18
187
5.4. WILL A REACTION OCCUR? 18
188
5.5. HOW FAST DOES A REACTION GO? 190
19
5.6. CLASSIFICATION OF CHEMICAL REACTIONS 190
19
5.7. QUANTITATIVE INFORMATION FROM CHEMICAL REACTIONS 19
193
Review of Quantitative Chemical Terms 19
193
Calcination of Limestone 19
194
5.8. WHAT IS STOICHIOMETRY AND WHY IS IT IMPORTANT? 195
19
The Mole Ratio Method of Stoichiometric Calculations 196
19
CHAPTER SUMMARY 200
20
Answers to Chapter Summary 20
202
QUESTIONS AND PROBLEMS 203
2

6. ACIDS, BASES, AND SALTS 209


6.1. THE IMPORTANCE OF ACIDS, BASES, AND SALTS 209
20
6.2. THE NATURE OF ACIDS, BASES, AND SALTS 210
21
Hydrogen Ion and Hydroxide Ion 210
21
Acids 21
210
Bases 211
21
Salts 211
21
Amphoteric Substances 21
212
Metal Ions as Acids 212
21
Salts That Act as Bases 213
21
Salts That Act as Acids 21
213
6.3. CONDUCTANCE OF ELECTRICITY BY ACIDS, BASES,
AND SALTS IN SOLUTION 21
214
Electrolytes 21
215
6.4. DISSOCIATION OF ACIDS AND BASES IN WATER 216
2
6.5. THE HYDROGEN ION CONCENTRATION AND BUFFERS 21
218
Buffers 219
21
6.6. pH
H AND THE RELATIONSHIP BETWEEN HYDROGEN ION
AND HYDROXIDE ION CONCENTRATIONS 21
219
Acid–Base Equilibria 221
22
6.7. PREPARATION OF ACIDS 222
22
6.8. PREPARATION OF BASES 22
223
6.9. PREPARATION OF SALTS 225
22

© 2009 by Taylor & Francis Group, LLC

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x Contents

6.10. ACID SALTS AND BASIC SALTS 22


227
Acid Salts 227
22
Basic Salts 22
227
6.11. WATER OF HYDRATION 22
227
6.12. NAMES OF ACIDS, BASES, AND SALTS 228
22
Acids 228
22
Bases 228
22
Salts 22
229
CHAPTER SUMMARY 23
232
Answers to Chapter Summary 233
23
QUESTIONS AND PROBLEMS 236
23

7. SOLUTIONS AND SOLVENTS 243


7.1. WHAT ARE SOLUTIONS? WHY ARE THEY IMPORTANT? 243
24
Reactions in Solution 24
244
Solutions in Living Systems 245
24
Solutions in the Environment 24
245
Industrial
Industrial Uses of Solutions 246
24
7.2. SOLVENTS 24
246
7.3. WATER—A UNIQUE SOLVENT 247
24
7.4. THE SOLUTION PROCESS AND SOLUBILITY 24
249
7.5. SOLUTION CONCENTRATIONS 251
25
Molar Concentration 25
252
Diluting Solutions 254
25
Molar Concentration of H⫹ Ion and pH 255
25
Solubility 256
25
7.6. STANDARD SOLUTIONS AND TITRATIONS 25
257
7.7. PHYSICAL PROPERTIES
PROPERTIES OF SOLUTIONS 25
259
Freezing Point Depression 259
25
Boiling Point Elevation 25
259
Osmosis 259
25
7.8. SOLUTION EQUILIBRIA 261
26
Solution Equilibria 26
261
Solubilities of Gases 26
263
7.9. COLLOIDAL SUSPENSIONS 265
2
Kinds of Colloidal Particles 26
265
Colloid Stability 26
266
Coagulation and Flocculation of Colloidal Particles 26
268
CHAPTER SUMMARY 268
26
Answers to Chapter Summary 270
27
QUESTIONS AND PROBLEMS 2
272

8. CHEMISTRY AND ELECTRICITY 275


8.1. CHEMISTRY AND ELECTRICITY 27
275
8.2. OXIDATION AND REDUCTION 276
27
8.3. OXIDATION–REDUCTION IN SOLUTION 279
27
8.4. THE DRY CELL 28
281
8.5. STORAGE BATTERIES 28
283

© 2009 by Taylor & Francis Group, LLC

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Contents xi

8.6. USING ELECTRICITY TO MAKE CHEMICAL REACTIONS OCCUR 28


286
Electrolysis of Water: A Green Technology 286
28
Electrolytic Manufacture of Chemicals 28
288
8.7. ELECTROPLATING 28
289
8.8. FUEL CELLS 290
29
8.9. SOLAR CELLS 29
291
8.10. REACTION TENDENCY 29
292
Measurement of E 0 293
29
E 0 Values and Reaction Tendency 29
294
8.11. EFFECT OF CONCENTRATION: NERNST EQUATION 29
296
8.12. POTENTIOMETRY 297
29
8.13. CORROSION 29
299
CHAPTER SUMMARY 300
30
Answers to Chapter Summary 302
30
QUESTIONS AND PROBLEMS 304
30

9. ORGANIC CHEMISTRY 307


9.1. ORGANIC CHEMISTRY 307
30
Molecular Geometry in Organic Chemistry 30
307
9.2. HYDROCARBONS 308
30
Alkanes 308
30
Alkenes and Alkynes 314
31
Alkenes and Cis–Trans Isomerism 315
31
Condensed Structural Formulas 315
31
Aromatic Hydrocarbons 316
31
9.3. ORGANIC FUNCTIONAL GROUPS AND CLASSES
OF ORGANIC COMPOUNDS 31
318
Organo-Oxygen Compounds 319
31
Organonitrogen Compounds 321
32
Organohalide Compounds 322
32
Organosulfur Compounds 326
32
Organophosphorus Compounds 32
328
9.4. SYNTHETIC POLYMERS 33
330
CHAPTER SUMMARY 332
33
Answers to Chapter Summary 334
33
SUPPLEMENTARY REFERENCES 33
335
QUESTIONS AND PROBLEMS 33
336

10. BIOLOGICAL CHEMISTRY 339


10.1. BIOCHEMISTRY 339
33
Biomolecules 34
340
10.2. BIOCHEMISTRY AND THE CELL 340
34
Major Cell Features 34
340
10.3. PROTEINS 34
342
Protein Structure 34
344
Denaturation of Proteins 346
34
10.4. CARBOHYDRATES 347
34
10.5. LIPIDS 349
34

© 2009 by Taylor & Francis Group, LLC

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xii Contents

10.6. ENZYMES 35
351
10.7. NUCLEIC ACIDS 355
35
Nucleic Acids in Protein Synthesis 358
35
Modified DNA 35
359
10.8. RECOMBINANT DNA AND GENETIC ENGINEERING 35
359
10.9. METABOLIC PROCESSES 36
360
Energy-Yielding Processes 360
36
CHAPTER SUMMARY 361
36
Answers to Chapter Summary 362
36
LITERATURE CITED 363
36
SUPPLEMENTARY REFERENCES 364
36
QUESTIONS AND PROBLEMS 364
36

INDEX 367

© 2009 by Taylor & Francis Group, LLC

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PREFACE

Fundamentals of Environmental Chemistry,


Chemistry, 3rd edition, is designed to build upon the approach
successfully employed in the first two editions while also expanding the scope of the book into the
strongly emerging area of Sustainability Science and Technology, which includes green chemistry
and industrial ecology. The book takes into account the needs of those who have little or no
knowledge of chemistry, but who require the basics of chemical science for their trade, profession,
or study curriculum, as well as for readers who want to have an understanding of the fundamentals
of sustainable chemistry and its crucial role in maintaining a livable planet.
The book are a basic course in chemical science that includes the fundamentals of organic
chemistry and biochemistry. In presenting the fundamentals, every effort is made to relate them to
real-world examples from environmental chemistry, green chemistry, and related areas while still
maintaining brevity and simplicity.
One of the unique features of the book is a “mini-course” in chemistry presented in the first
few pages of Chapter 1 and consisting of the most basic concepts and terms needed by the reader to
really begin to understand chemistry. To study chemistry, it is necessary to know a few of the essen-
tials, i.e., what an atom is and what is meant by elements, chemical formulas, chemical bonds,
molecular mass, and chemical reactions. With these terms defined in very basic ways, it is then pos-
sible to go into greater detail concerning chemical concepts without having to assume—as many
introductory chemistry books do somewhat awkwardly—that the reader knows the meaning of
these terms.
Chapter 2 discusses matter largely on the basis of its physical nature and behavior, and intro-
duces physical and chemical properties, states of matter, the mole as a quantity of matter, and other
ideas required to visualize chemical substances as physical entities. Chapters 3–5 cover the core of
chemical knowledge constructed as a language in which the elements and the atoms that form them
(Chapter 3) are presented as letters of an alphabet, the compounds made up from the elements
(Chapter 4) are analogous to words, the reactions by which compounds are synthesized and changed
(Chapter 5) are like sentences in the chemical language, and the mathematical aspects hold it all
together quantitatively. Chapters 6–8 constitute the remainder of the material that is usually regarded
as essential in general chemistry. A basic coverage of organic chemistry is presented in Chapter 9.
Although this topic is often omitted at the beginning chemistry level, those who deal with the real
world of environmental pollution, hazardous wastes, agricultural science, and other applied areas
quickly realize that a rudimentary understanding of organic chemistry is required. Chapter 10 covers
biological chemistry, an area essential to understanding material presented in later chapters that
deal with environmental and toxicological chemistry.
The author welcomes input from readers. Comments and questions may be sent to the author
at the following e-mail address: [email protected]

© 2009 by Taylor & Francis Group, LLC

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© 2009 by Taylor & Francis Group, LLC

K10124_C000.indd xiv 2/4/2009 8:42:00 PM


AUTHOR

Stanley E. Manahan is a professor of chemistry at the University of Missouri (Columbia) where


he has been on the faculty since 1965. He received his A.B. in chemistry from the Emporia State
University in 1960 and his PhD in analytical chemistry from the University of Kansas in 1965.
Since 1968, his primary research and professional activities have been in environmental chemistry,
toxicological chemistry, waste gasification, and gasification of biomass for energy production.
His classic textbook, Environmental Chemistry
Chemistry,, 8th edition (CRC Press, Boca Raton, Florida,
2004), has been in print continuously in various editions since 1972 and is the longest standing title
on this subject in the world. Other books that he has written are Green Chemistry and the Ten
Commandments of Sustainability
Sustainability,, 2nd edition (ChemChar Research, Inc., 2006), Green Science
and Technology: The Path to a Sustainable Future Future,, 2nd edition (CRC Press/Taylor & Francis,
2006), Toxicological Chemistry and Biochemistry,
Biochemistry, 3rd edition (CRC Press/Lewis Publishers,
2001), Industrial Ecology: Environmental Chemistry and Hazardous Waste (CRC Press/Lewis
Publishers, 1999), Environmental Science and Technology (CRC Press/Lewis Publishers, 1997),
Hazardous Waste Chemistry, Toxicology and Treatment (Lewis Publishers, 1992), Quantitative
Chemical Analysis
Analysis,, (Brooks/Cole, 1986), and General Applied Chemistry
Chemistry,, 2nd edition (Willard
Grant Press, 1982).
Dr. Manahan has lectured on the topics of environmental chemistry, toxicological chemistry,
waste treatment, and green chemistry throughout the U.S. as an American Chemical Society Local
Section Tour Speaker. He has also presented plenary lectures on these topics at international
meetings in Puerto Rico, the University of the Andes in Mérida in Venezuela, Hokkaido University
in Japan, the National Autonomous University in Mexico City, and in Italy and France. Since 1998,
he has taught a short course annually at the National Autonomous University of Mexico. He was
the recipient of the Year 2000 Award of the Environmental Chemistry Division of the Italian
Chemical Society.

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1. INTRODUCTION TO CHEMISTRY AND
GREEN CHEMISTRY

1.1. IF WE DO NOT CHANGE DIRECTION

An old Chinese proverb states, “If we do not change direction, we are likely to
end up where we are headed.” At no time has this statement been more appropriate
than as it applies to humankind at the present time. Blessed with a miniscule, but
unique and remarkable, speck of the universe that has conditions conducive to life,
humans are on a course that, if not altered, will result in destruction of the only
home that they have or ever can have. About 2 billion years ago, one other type
of organism, photosynthetic cyanobacteria, used captured solar energy to produce
biomass and liberate atmospheric elemental oxygen to the atmosphere, making
possible all of the life forms that require this gas for their metabolic processes.
This was a planet-altering process that determined the life forms that have existed
on Earth in all the eons since it occurred and that caused massive chemical
change, such as the formation of iron oxide deposits from the oxidation of soluble
iron in water. Until now, no type of organism has caused such a drastic change on
Earth, particularly in its atmosphere. However, by burning enormous quantities
of fossil fuels at an ever-increasing rate, humans are well on the way to doubling
pre-industrial levels of atmospheric carbon dioxide. Virtually all reputable authori-
ties agree that this will have a significant warming effect on the global climate.
Whereas the atmosphere created by the humble single-celled cyanobacteria made
possible the development of millions of kinds of new species, what humans are
doing to the climate now will almost certainly result in the extinction of hundreds of
thousands—perhaps millions—of species.
The challenge facing humankind today is sustainability
sustainability,, the maintenance and
enhancement of conditions that will enable humans and other organisms to exist on
Planet Earth. This means living within the limits of materials extracted from Earth
or taken from its atmosphere or oceans. It means, especially, dealing sustainably
with energy, essential to modern civilizations, but, with the present reliance on fossil
fuels that pump global-warming carbon dioxide into the atmosphere, unsustainable
with present patterns of acquisition and use.

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2 Fundamentals of Sustainable Chemical Science

So, collectively, humankind faces a monumental challenge. It is relatively easy to


see the enormous problems that face us. It is also easy for some to debunk what they
consider to be alarmist rhetoric and to contend that doubling the small fraction of a
percent of carbon dioxide in the atmosphere within a few decades cannot possibly
seriously damage Earth’s carrying capacity or that cropland is so abundant and can be
made so productive that diverting a significant portion of it to the intensive cultivation
of corn-based ethanol fuel cannot have a significant adverse effect on world food
production. Others contend that the situation is hopeless and that, in a world in which
people of similar heritage who differ mainly in details of their creeds persist in trying
to kill each other, it is futile to even try to get Earth’s diverse peoples to cooperate on
a global scale to ensure sustainability. Evidence is mounting against the deniers. It is a
fact that glaciers are melting at a pace never before seen in the time over which historical
records exist. It is a fact that people in cities in the far Southern Hemisphere over
which the Antarctic ozone hole spreads during the early spring months of September
and October find it necessary to take protective measures to prevent debilitating expo-
sure to ultraviolet radiation that penetrates the stratospheric ozone layer thinned by the
effects of chlorofluorocarbon (Freon) compounds. It is a fact that fluctuating prices of
gasoline show that limits are being reached on available resources of petroleum.
As a result of the challenges facing humankind and its relationship with Planet
Earth, thoughtful people have begun to take action to try to ensure their survival and
that of their descendents. Measures to prevent loss of essential Earth support systems
have been ongoing in some sectors for quite some time. By 1900, it was recognized
that the cultivation of soil in the U.S. that had lain undisturbed until the arrival of
European settlers was causing unacceptable soil erosion. The great damage caused to
former prairie lands of the U.S. Great Plains by drought and wind erosion during the
dustbowl days of the 1930s led to intensive government-funded initiatives in soil con-
servation. Rachel Carson’s classic 1962 book Silent Spring brought to public attention
the damage caused to wildlife by the indiscriminate use of persistent pesticides and
helped bring about the massive environmental improvement efforts of much of the
world in the latter part of the 20th century. By around 2000, the environmental move-
ment had developed an emphasis upon sustainability and self-regulating systems for
environmental preservation. Industrial ecology, which treats industrial enterprises as
mutually beneficial interacting systems analogous to species in natural ecosystems,
had emerged as a dynamic discipline. Since the mid-1990s, there has been a strong
“green” movement in which human enterprises are dedicated to environmental
protection, efficient uses of materials and energy, maximum recycling, and minimum
generation of waste. Now many individuals and enterprises are dedicated to green
engineering and, specifically in chemistry, to green chemistry.

1.2. THE ESSENTIAL ROLE OF CHEMISTRY

Chemistry is unavoidable. We eat chemicals. We are made of chemicals. We are


surrounded by chemicals. All of these things are true because chemistry is the

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Introduction to Chemistry and Green Chemistry 3

science of matter; all things are chemical. Therefore, chemistry deals with the air we
breathe, the water we drink, the soil that grows our food, and vital life substances
and processes. Our own bodies contain a vast variety of chemical substances and are
tremendously sophisticated chemical factories that carry out an incredible number
of complex chemical processes.
There is a tremendous concern today about the uses—and particularly the
misuses—of chemistry as it relates to the environment. Ongoing events serve as
constant reminders of threats to the environment ranging from individual expo-
sures to toxicants to phenomena on a global scale that may cause massive, perhaps
catastrophic, alterations in climate as discussed above. These include, as examples,
air quality in Beijing so bad that it raised concerns over the health of athletes in
the 2008 Summer Olympics, pets dying from consumption of food illegally laced
with toxic melamine put into animal food to artificially raise its nitrogen content
(used as a measure of protein), and tanks of toxic chlorine gas combined with ter-
rorist explosives to add to the toll and misery caused by these diabolical devices
in Iraq. Furthermore, large numbers of employees must deal with hazardous
substances and wastes in laboratories and the workplace. All such matters
involve chemistry for understanding of the problems and for arriving at solutions
to them.
The central role that chemistry must play in dealing with the challenges facing
humankind and its stewardship of Planet Earth is undeniable. People in a large
variety of areas and enlightened citizens need to have some basic knowledge of
chemistry. The purpose of this book is to provide such knowledge for a broad range
of people who want and need it. The book presents an overview of chemistry,
including organic chemistry (Chapter 9) and biological chemistry (Chapter 10), at
a fundamental level. The book relates to sustainability science, environmental
chemistry, and green chemistry.

1.3. ENVIRONMENTAL CHEMISTRY AND


GREEN CHEMISTRY

Environmental chemistry is that branch of chemistry that deals with the origins,
transport, reactions, effects, and fates of chemical species in the water, air, earth,
and living environments and the influence of human activities thereon.1 A related
discipline, toxicological chemistry, is the chemistry of toxic substances with emphasis
upon their interaction with biologic tissue and living systems.2 Besides being an
essential, vital discipline in its own right, environmental chemistry provides an excel-
lent framework for the study of chemistry, dealing with “general chemistry,” organic
chemistry, chemical analysis, physical chemistry, photochemistry, geochemistry,
and biological chemistry.
In its earlier stages of development dating from around the 1960s, the emphasis
in environmental chemistry was upon detection of pollution, cataloging its adverse
effects, and controlling pollutants once they were produced. This resulted in an

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4 Fundamentals of Sustainable Chemical Science

Figure 1.1. Illustration of the definition of green chemistry.

abundance of laws and regulations in countries throughout the world that, in many
areas, prevented pollution from becoming worse and in a number of cases improved
air and water quality and controlled toxic and hazardous substances improperly
disposed on or buried beneath Earth’s surface. Even as these efforts gained success,
it became obvious that such measures were increasingly expensive to implement as
allowable pollutant levels became lower. The “command-and-control” approach was
hard to monitor and potential polluters were always tempted to avoid controls to save
costs. A better way was needed. Insofar as chemistry was concerned, a better way
emerged in the practice of green chemistry.
Formulated in the latter 1990s by Paul Anastas and others, green chemistry is
the practice of chemical science and engineering in ways that minimize consump-
tion of materials and energy, produce the least possible amount of waste, and is
inherently safe.3 Figure 1.1 illustrates this definition of green chemistry. Ideally,
green chemistry is practiced within a framework of industrial ecology
ecology,, defined as a
comprehensive approach to production, distribution, utilization, and termination of
goods and services in a manner that maximizes mutually beneficial utilization of
materials and energy while preventing the production of wastes and pollutants.4
Within the short time that it has been recognized as a distinct area of endeavor,
green chemistry has become an integral, important part of the practice of chemical
science.

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Introduction to Chemistry and Green Chemistry 5

1.4. A MINI-COURSE IN CHEMISTRY

It is much easier to learn chemistry if one already knows some chemistry! That
is, in order to go into any detail on any chemical topic, it is extremely helpful to have
some very rudimentary knowledge of chemistry as a whole. For example, a crucial
part of chemistry is an understanding of the nature of chemical compounds, the
chemical formulas used to describe them, and the chemical bonds that hold them
together; these are topics addressed in Chapter 4 of this book. However, to under-
stand these concepts, it is very helpful to know some things about the chemical reac-
tions by which chemical compounds are formed, as addressed in Chapter 5. To work
around this problem, Chapter 1 provides a highly condensed, simplified, but mean-
ingful overview of chemistry to give the reader the essential concepts and terms
required to understand more advanced chemical material.

1.5. THE BUILDING BLOCKS OF MATTER

All matter is composed of only about a hundred fundamental kinds of matter


called elements
elements.. Each element is made up of very small entities called atoms
atoms;; all
atoms of the same element behave identically chemically. The study of chemistry,
therefore, can logically begin with elements and the atoms of which they are
composed.

Subatomic Particles and Atoms

Figure 1.2 represents an atom of deuterium, a form of the element hydrogen.


It is seen that such an atom is made up of even smaller subatomic particles—
particles
positively charged protons
protons,, negatively charged electrons
electrons,, and uncharged (neutral)

Nucleus

+ n Electron “cloud”

Figure 1.2. Representation of a deuterium atom. The nucleus contains one proton (()) and one
neutron (n). The electron (()) is in constant, rapid motion around the nucleus, forming a cloud of nega-
tive electrical charge, the density of which drops off with increasing distance from the nucleus.

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6 Fundamentals of Sustainable Chemical Science

neutrons. Protons and neutrons have relatively high masses compared with electrons
and are contained in the positively charged nucleus of the atom. The nucleus has
essentially all the mass, but occupies virtually none of the volume, of the atom. An
uncharged atom has the same number of electrons as protons. The electrons in an
atom are contained in a cloud of negative charge around the nucleus that occupies
most of the volume of the atom.

Atoms and Elements

All of the literally millions of different substances are composed of only around
100 elements. Each atom of a particular element is chemically identical to every
other atom and contains the same number of protons in its nucleus. This number
of protons in the nucleus of each atom of an element is the atomic number of the
element. Atomic numbers are integers ranging from 1 to more than 100, each of
which denotes a particular element. In addition to atomic numbers, each element has
a name and a chemical symbol
symbol,, such as carbon, C; potassium, K (for its Latin name
kalium); or cadmium, Cd. In addition to atomic number, name, and chemical symbol,
each element has an atomic mass (atomic weight). The atomic mass of each element
is the average mass of all atoms of the element, including the various isotopes of
which it consists. The atomic mass unitunit,, u (also called the dalton), is used to express
dalton),
masses of individual atoms and molecules (aggregates of atoms). These terms are
illustrated for carbon and nitrogen in Figure 1.3.
Although atoms of the same element are chemically identical, atoms of most
elements consist of two or more isotopes that have different numbers of neutrons in

– – –

6+ 7+ –
– – – –
6n 7n

– – – –

An atom of carbon, symbol C. An atom of nitrogen, symbol N.


Each C atom has 6 protons (+) Each N atom has 7 protons (+)
in its nucleus, so the atomic in its nucleus, so the atomic
number of C is 6. The atomic number of N is 7. The atomic
mass of C is 12. mass of N is 14.

Figure 1.3. Atoms of carbon and nitrogen.

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Introduction to Chemistry and Green Chemistry 7

Table 1.1. Some of the More Important Common Elements


Atomic Atomic Mass (Relative
Element Symbol Number to Carbon-12)
Argon Ar 18 39.948
Bromine Br 35 79.904
Calcium Ca 20 40.08
Carbon C 6 12.01115
Chlorine Cl 17 35.453
Copper Cu 29 63.546
Fluorine F 9 18.998403
Helium He 2 4.00260
Hydrogen H 1 1.0080
Iron Fe 26 55.847
Magnesium Mg 12 24.305
Mercury Hg 80 200.59
Neon Ne 10 20.179
Nitrogen N 7 14.0067
Oxygen O 8 15.9994
Potassium K 19 39.0983
Silicon Si 14 28.0855
Sodium Na 11 22.9898
Sulfur S 16 32.06

their nuclei. Some isotopes are radioactive isotopes or radionuclides


radionuclides,, which have
unstable nuclei that give off charged particles and gamma rays in the form of radio-
activity.. This process of radioactive decay changes atoms of a particular element
activity
into atoms of another element.
Throughout this book, reference is made to various elements. A list of the known
elements is at the end of Chapter 3. Fortunately, most of the chemistry covered in this
book requires familiarity with only about 25–30 elements. An abbreviated list of a
few of the most important elements that the reader should learn at this point is given
in Table 1.1.

The Periodic Table

When elements are considered in order of increasing atomic number, it is


observed that their properties are repeated in a periodic manner. For example,
elements with atomic numbers 2, 10, and 18 are gases that do not undergo chemical

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8 Fundamentals of Sustainable Chemical Science

IA Noble Gases
1 18
1 2
1 H IIA IIIA IVA VA VIA VIIA He
1.008 2 Transition Elements 13 14 15 16 17 4.003
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
VIII
11 12 13 14 15 16 17 18
3 Na Mg IIIB IVB VB VIB VIIB IB IIB Al Si P S Cl Ar
22.99 24.3 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.07 35.45 39.95
Period

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.39 69.72 72.59 74.92 78.96 79.9 83.8
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 98.91 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 (210) (210) (222)
87 88 89 104 105 106 107 108 109
7 Fr Ra Ac * Rf Ha Sg Ns Ha Mt
(223) (226) (227) * (261) (262) (263) (262) (265) (266)

Inner Transition Elements


58 59 60 61 62 63 64 65 66 67 68 69 70 71
Lanthanide series * Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
6 140.1 140.9 144.2 144.9 150.4 152.0 157.2 158.9 162.5 164.9 167.3 168.9 173.0 175.0
* 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Actinide series * Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
7 232.0 231.0 238.0 237.0 239.1 243.1 247.1 247.1 252.1 252.1 257.1 256.1 259.1 260.1

Figure 1.4. The periodic table of the elements.

reactions and consist of individual molecules, whereas those with atomic numbers
larger by one—3, 11, and 19—are unstable, highly reactive metals. An arrangement
of the elements in a manner that reflects this recurring behavior is known as the
periodic table (Figure 1.4). The periodic table is extremely useful in understanding
chemistry and predicting chemical behavior. The entry for each element in the periodic
table gives the element’s atomic number, symbol, and atomic mass. More-detailed
versions of the table include each element name and other information as well.

Features of the Periodic Table

The periodic table gets its name from the fact that the properties of elements
are repeated periodically in going from left to right across a horizontal row of
elements. The table is arranged such that an element has properties similar to those
of other elements above or below it in the table. Elements with similar chemical
properties are called groups of elements and are contained in vertical columns in
the periodic table.

1.6. CHEMICAL BONDS AND COMPOUNDS

Only a few elements, particularly the noble gases, exist as individual atoms; most
atoms are joined by chemical bonds to other atoms. This can be illustrated very simply
by elemental hydrogen, which exists as molecules
molecules,, each consisting of 2 H atoms
linked by a chemical bond as shown in Figure 1.5. Because hydrogen molecules
contain 2 H atoms, they are said to be diatomic and are denoted by the chemical
formula H2. The H atoms in the H2 molecule are held together by a covalent bond

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Introduction to Chemistry and Green Chemistry 9

H
H H H H2

The H atoms in are held together by that have the


elemental hydrogen chemical bonds in molecules chemical formula H2.

Figure 1.5. Molecule of H2.

made up of 2 electrons, each contributed by one of the H atoms, and shared between
the atoms.
As discussed in latter parts of this book, chemical bonds are extremely important
in environmental chemistry and green chemistry. For example, the very strong bonds
between atoms of carbon and those of oxygen in the compound carbon dioxide are
responsible for the high stability of this gas in Earth’s atmosphere, enabling it to
persist and contribute to “greenhouse” warming of the atmosphere. The relatively
weak bonds between nitrogen and oxygen in air-pollutant nitrogen dioxide make
this compound susceptible to breaking apart when it absorbs radiation from the Sun,
leading to reactive free oxygen atoms that start the process by which photochemical
smog is formed.

Chemical Compounds

Most substances consist of two or more elements joined by chemical bonds. As


an example, consider the chemical combination of the elements hydrogen and
oxygen shown in Figure 1.6. Oxygen, chemical symbol O, has an atomic number of
8 and an atomic mass of 16.00 and exists in the elemental form comprising about
20% of air as diatomic molecules of O2, each composed of two atoms of oxygen
joined by a chemical bond. Hydrogen atoms combine with oxygen atoms to form
molecules in which 2 H atoms are bonded to 1 O atom in a substance with the
chemical formula H2O (water). A substance such as H2O that consists of a chemi-
cally bonded combination of two or more elements is called a chemical compound
compound..
(A chemical compound is a substance that consists of atoms of two or more different
elements bonded together.) In the chemical formula for water, the letters H and O

H
H H

H O H 2O
O

Hydrogen atoms and to form molecules in The chemical formula of


oxygen atoms bond which 2 H atoms are the resulting compound,
together attached to 1 O atom. water, is H2O.

Figure 1.6. A molecule of water, H2O, formed from 2 H atoms and 1 O atom held together by
chemical bonds.

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10 Fundamentals of Sustainable Chemical Science

are the chemical symbols of the two elements in the compound and the subscript 2
indicates that there are 2 H atoms per O atom. (The absence of a subscript after the
O denotes the presence of just 1 O atom in the molecule.) Each of the chemical
bonds holding a hydrogen atom to the oxygen atom in the water molecule is com-
posed of two electrons shared between the hydrogen and oxygen atoms.

Ionic Bonds

As shown in Figure 1.7, the transfer of electrons from one atom to another
produces charged species called ions ions.. Positively charged ions are called cations and
negatively charged ions are called anions
anions.. Ions that make up a solid compound are
held together by ionic bonds in a crystalline lattice consisting of an ordered arrange-
ment of the ions in which each cation is largely surrounded by anions and each anion
by cations. The attracting forces of the oppositely charged ions in the crystalline
lattice constitute the ionic bonds in the compound.
The formation of the ionic compound magnesium oxide is shown in Figure 1.7.
In naming this compound, the cation is simply given the name of the element from
which it was formed, magnesium. However, the ending of the name of the anion,
oxide
ox ide,, is different from that of the element from which it was formed, oxygen
oxygen.
Rather than individual atoms that have lost or gained electrons, many ions are
groups of atoms bonded together covalently and having a net charge. A common
example of such an ion is the ammonium ion, NH4

H +
H N H Ammonium ion, NH 4 +
H
consisting of 4 hydrogen atoms covalently bonded to a single nitrogen (N) atom and
having a net electrical charge of 1
1 for the whole cation.

2e– Mg2+ ion O2– ion

12e– 8e– 10e– 10e–

Mg O Mg O
12+ 8+ 12+ 8+

MgO
Atom nucleus
The transfer of two electrons from yields an ion of Mg2+ and one of
an atom of Mg to an O atom O2– in the compound MgO

Figure 1.7. Ionic bonds are formed by the transfer of electrons and the mutual attraction of
oppositely charged ions in a crystalline lattice.

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Introduction to Chemistry and Green Chemistry 11

Summary of Chemical Compounds and the Chemical Bond

The preceding several pages have just covered some material on chemical
compounds and bonds that are essential to understand chemistry. To summarize,
these are as follows:

• Atoms of two or more different elements can form chemical bonds


with each other to yield a product that is entirely different from the
elements.
• Such a substance is called a chemical compound.
compound
• The formula of a chemical compound gives the symbols of the elements
and uses subscripts to show the relative numbers of atoms of each element
in the compound.
• Molecules of some compounds are held together by covalent bonds
consisting of shared electrons.
• Another kind of compound consists of ions composed of electrically
charged atoms or groups of atoms held together by ionic bonds that exist
because of the mutual attraction of oppositely charged ions.

Molecular Mass

The average mass of all molecules of a compound is its molecular mass


(formerly called molecular weight). The molecular mass of a compound is calcu-
lated by multiplying the atomic mass of each element by the relative number
of atoms of the element, then adding all the values obtained for each element in
the compound. For example, the molecular mass of NH3 is 14.0  3  1.0  17.0.
As another example consider the following calculation of the molecular mass of
ethylene (C2H4):

1. The chemical formula of the compound is C2H4.


2. Each molecule of C2H4 consists of 2 C atoms and 4 H atoms.
3. From the periodic table or Table 1.1, the atomic mass of C is 12.0 and that
of H is 1.0.
4. Therefore, the molecular mass of C2H4 is

12.0 + 12.0 + 1.0 + 1.0 + 1.0 + 1.0 = 28.0


From 2 C atoms From 4 H atoms

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12 Fundamentals of Sustainable Chemical Science

1.7. CHEMICAL REACTIONS AND EQUATIONS

Chemical reactions occur when substances are changed to other substances


through the breaking and formation of chemical bonds. For example, water is produced
by the chemical reaction of hydrogen and oxygen:

Hydrogen plus oxygen yields water

Chemical reactions are written as chemical equations. The chemical reaction


between hydrogen and water is written as the balanced chemical equation

2H2  O2 Æ 2H2O (1.7.1)

in which the arrow is read as “yields” and separates the hydrogen and oxygen reac-
tants from the water product
product.. Note that because elemental hydrogen and elemental
oxygen occur as diatomic molecules of H2 and O2, respectively, it is necessary to
write the equation in a way that reflects these correct chemical formulas of the
elemental form. All correctly written chemical equations are balanced
balanced,, in that they
must show the same number of each kind of atom on both sides of the equation
equation.. The
equation above is balanced because of the following:

On the left
• There are 2 H2 molecules,
molecules, each containing 2 H atoms for a total of 4 H
atoms on the left.
• There is 1 O2 molecule,
molecule, containing 2 O atoms for a total of 2 O atoms on
the left.

On the right
• There are 2 H2O molecules each containing 2 H atoms and 1 O atom for a
total of 4 H atoms and 2 O atoms on the right.

The process of balancing chemical equations is relatively straightforward for simple


equations. It is discussed in Chapter 4.

1.8. NUMBERS IN CHEMISTRY: EXPONENTIAL NOTATION

An essential skill in chemistry is the ability to handle numbers, including very


large and very small numbers. An example of the former is Avogadro’s number,
which is discussed in detail in Chapters 2 and 3. Avogadro’s number is a way of
expressing quantities of entities such as atoms or molecules and is equal to approxi-
mately 602 000 000 000 000 000 000 000. A number so large written in this decimal
form is very cumbersome to express and very difficult to handle in calculations.
It can be expressed much more conveniently in exponential notation. Avogadro’s

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Introduction to Chemistry and Green Chemistry 13

Table 1.2. Numbers in Exponential and Decimal Form


Places Decimal
Moved for Decimal
Exponential Form of Number Decimal Form Form
1.37  105  1.37  10  10  10  10  10 Æ 5 places 137 000

7.19  107  7.19  10  10  10  10  10  10  10 Æ 7 places 71 900 000


3.25  102  3.25/(10  10) ¨ 2 places 0.0325
2.6  106  2.6/(10  10  10  10  10  10) ¨ 6 places 0.000 0026
5.39  105  5.39/(10  10  10  10  10) ¨ 5 places 0.000 0539

number in exponential notation is 6.02  1023. It is put into decimal form by moving
the decimal in 6.02 to the right by 23 places. Exponential notation works equally
well to express very small numbers, such as 0.000 000 000 000 000 087. In expo-
nential notation, this number is 8.7  1017
17. To convert this number back to decimal

form, the decimal point in 8.7 is simply moved 17 places to the left.
A number in exponential notation consists of a digital number equal to or greater
than exactly 1 and less than exactly 10 (e.g., 1.00000, 4.3, 6.913, 8.005, and 9.99999)
multiplied by a power of 10 (e.g., 1017
17, 1013, 105, 103, and 1023). Some examples of

numbers expressed in exponential notation are given in Table 1.2. As can be seen in
the second column of the table, a positive power of 10 shows the number of times
that the digital number is multiplied by 10 and a negative power of 10 shows the
number of times that the digital number is divided by 10.

Addition and Subtraction of Exponential Numbers

An electronic calculator keeps track of exponents automatically and with total


accuracy. For example, getting the sum 7.13  103  3.26  104 on a calculator
simply involves the following sequence:

7.13 EE3 + 3.26 EE4 = 3.97 EE4

where 3.97 EE4 stands for 3.97  104. To do such a sum manually, the largest number
in the sum should be set up in the standard exponential notation form and each of the
other numbers should be taken to the same power of 10 as that of the largest number
as shown below for the calculation of 3.07  102  6.22  103  4.14  104:

3.07  102 (largest number, digital portion between 1 and 10)


0.622
0.622  102 (same as 6.22  103)
0.041  103 (same as 4.1  104)
0.041
–––––––––––––––––––––––––––––––
Answer::
Answer 2.49  102.

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14 Fundamentals of Sustainable Chemical Science

Multiplication and Division of Exponential Numbers

As with addition and subtraction, multiplication and division of exponential


numbers on a calculator or computer are simply a matter of (correctly) pushing
buttons. For example, to solve
1.39  102  9.05  108
______________________
3.11  104
on a calculator, the sequence below is followed:

1.39 EE-2 × 9.05 EE8 3.11 EE4 = 4.04 EE2 (same as 4.04 × 102)

In multiplication and division of exponential numbers, the digital portions of the


numbers are handled conventionally. For the powers of 10 in multiplication exponents
are added algebraically, whereas in division the exponents are subtracted algebrai-
cally. Therefore, in the preceding example,
1.39  102  9.05  108
______________________
3.11  104
the digital portion is
1.39  9.05  4.04
__________
3.11
and the exponential portion is
102  108  102
__________
104
So the answer is 4.04  102.

Example: Perform the calculation below without using the exponential


Example:
notation feature of the calculator:
7.39  102  4.09  105
______________________
2.22  104  1.03  103
Answer:
Answer
Exponent of answer = –2 + 5 – (4 – 3) = 2

Algebraic addition of Algebraic subtraction of


exponents in the numerator exponents in the denominator

Answer  13.2  102  1.32  103


Example:: Solve
Example
3.49  103
___________________________________
3.26  1018  7.47  105  6.18  108
Answer:: 2.32  104.
Answer

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Introduction to Chemistry and Green Chemistry 15

1.9. SIGNIFICANT FIGURES AND UNCERTAINTIES IN NUMBERS

The preceding section illustrated how to handle very large and very small
numbers with exponential notation
notation.. This section considers uncertainties in num-
bers, taking into account the fact that numbers are known only to a certain degree
of accuracy
accuracy.. The accuracy of a number is shown by how many significant figures
or significant digits it contains. This can be illustrated by considering the atomic
masses of elemental boron and sodium. The atomic mass of boron is given as
10.81. Written in this way, the number expressing the atomic mass of boron con-
tains four significant digits—the 1, the 0, the 8, and the 1. It is understood to have
an uncertainty of  or 1 1 in the last digit, meaning that it is really 10.81 ± 0.01.
The atomic mass of sodium is given as 22.98977, a number with seven significant
digits understood to mean 22.98977 ± 0.00001. Therefore, the atomic mass of
sodium is known with more certainty than that of boron. The atomic masses in
Table 1.1 reflect the fact that there is less variability in atomic masses of some
elements as they occur in nature (due to variable distributions of elemental
isotopes), so that their atomic masses are known with much more certainty (e.g.,
fluorine, 18.998403) than is the case for others (e.g., calcium listed with an atomic
mass of 40.08).
The rules for expressing significant digits are summarized in Table 1.3. It is
important to express numbers to the correct number of significant digits in chemi-
cal calculations and in the laboratory. The use of too many digits implies an
accuracy in the number that does not exist and is misleading. The use of too few
significant digits does not express the number to the degree of accuracy to which
it is known.

Exercise: Referring to Table 1.3, give the number of significant digits and
the rule(s) upon which they are based for each of the following numbers:

(a) 17.000 (b) 9.5378 (c) 7.001 (d) $50


(e) 0.00300 (f) 7400 (g) 6.207  107 (h) 13.5269184
(i) 0.05029
Answers: (a) 5, Rule 4; (b) 5, Rule 1; (c) 4, Rule 2; (d) exact number;
Answers:
(e) 3, Rules 3 and 4; (f) uncertain, Rule 5; (g) 4, Rule 6; (h) 9, Rule 1;
(i) 4 Rules 2 and 3.

Significant Figures in Calculations

After numbers are obtained by a laboratory measurement, they are normally


subjected to mathematical operations to get the desired final result. It is important
that the answer have the correct number of significant figures. It should not have
so few that accuracy is sacrificed or so many that an unjustified degree of accuracy

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16 Fundamentals of Sustainable Chemical Science

Table 1.3. Rules for Use of Significant Digits


Example Number of
Number Significant Digits Rule
11.397 5 1. Nonzero digits in a number are always significant. The 1,
1, 3, 9, and 7 in this number are each significant
140.039 6 2. Zeros between nonzero digits are significant. The
1, 4, 0, 0, 3, and 9 in this number are each significant
0.00329 3 3. Zeros to the left of the first nonzero digit are not
significant, because they are used only to locate
the decimal point. Only 3, 2, and 9 in this number
are significant
70.00 4 4. Zeros to the right of a decimal point that are preceded
by a significant figure are significant. All three 0s,
as well as the 7, are significant
32 000 Uncertain 5. The number of significant digits in a number with zeros
to the left but not to the right of a decimal point (1700,
110 000) may be uncertain. Such numbers should be
written in exponential notation
3.20  103 3 6. The number of significant digits in a number written in
exponential notation is equal to the number of significant
digits in the decimal portion
Exactly 50 Unlimited 7. Some numbers, such as the amount of money that one
expects to receive when cashing a check or the number of
children claimed for income tax exemptions, are defined
as exact numbers without any uncertainty.

is implied. The two major rules that apply, one for addition/subtraction, the other for
multiplication/division, are the following:
1. In addition and subtraction, the number of digits retained to the right of the
decimal point should be the same as those in the number in the calculation
with the fewest such digits.
For example, 273.591  1.00327  229.13  503.72427 is rounded to
503.72 because 229.13 has only two significant digits beyond the decimal;
and 313.4  11.0785  229.13  553.6085 is rounded to 553.6 because
313.4 has only one significant digit beyond the decimal.
2. The number of significant figures in the result of multiplication/division
should be the same as that in the number in the calculation having the
fewest significant figures. For example,
3.7218  4.019  103  1.0106699  102
____________________
1.48

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Introduction to Chemistry and Green Chemistry 17

is rounded to 1.01 (3 significant figures because 1.48 has only 3 signifi-


cant figures); and
5.28721  107  7.245  105  3.802747533  103
__________________________
1.00732
is rounded to 3.803  103 (4 significant figures because 7.245 has only 4
significant figures).

It should be noted that an exact number is treated in calculations as though


it has an unlimited number of significant figures.

Exercise: Express each of the following to the correct number of signi-


Exercise:
ficant figures:

(a) 13.1  394.0000  8.1937 (b) 1.57  104  7.198  102


(c) 189.2003  13.47  2.563 (d) 221.9  54.2  123.008
603.9  21.7  0.039217
(e) _____________________ 3.1789  103  7.000032  104
(f) ___________________________
87 27.130921
(g) 100  0.7428  6.82197 (where 100 is an exact number)
Answers: (a) 415.3; (b) 1.13  105; (c) 173.17; (d) 1.48  106; (e) 5.9;
Answers:
(f) 8.2019; (g) 506.7.

Rounding Numbers

With an electronic calculator, it is easy to obtain a long string of digits that must
be rounded to the correct number of significant figures. The rules for doing this are
the following:

1. If the digit to be dropped is 0, 1, 2, 3, or 4, leave the last retained digit


unchanged:
Example: Round 4.17821 to 4 significant digits
Answer : 4.178
Last retained digit Digit to be dropped

2. If the digit to be dropped is 5, 6, 7, 8, or 9, increase the last retained digit by 1:


Example: Round 4.17821 to 3 significant digits
Answer: 4.18
Last retained digit Digit to be dropped

Use of Three Significant Digits

It is possible to become thoroughly confused about how many significant figures


to retain in an answer. In such a case, it is often permissible to use 3 significant figures.

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18 Fundamentals of Sustainable Chemical Science

Generally, this gives sufficient accuracy without doing grievous harm to the concept
of significant figures.

1.10. MEASUREMENTS AND SYSTEMS OF MEASUREMENT

The development of chemistry has depended strongly upon careful measure-


ments. Historically, measurements of the quantities of substances reacting and
produced in chemical reactions have allowed the explanation of the fundamental
nature of chemistry. Exact measurements continue to be of the utmost importance
in chemistry, and are facilitated by increasingly more sophisticated instrumentation.
For example, atmospheric chemists can determine a small degree of stratospheric
ozone depletion by measuring minute amounts of ultraviolet radiation absorbed by
ozone with satellite-mounted instruments. Determinations of a part per trillion or
less of a toxic substance in water may serve to trace the source of a hazardous pol-
lutant. This section discusses the basic measurements commonly made in chemistry
and environmental chemistry.

SI Units of Measurement

Several systems of measurement are used in chemistry and environmental


chemistry. The most systematic of these is the International System of Units
d’Unités), abbreviated SI
(Système Internationale d’Unités), SI,, a self-consistent set of units
based upon the metric system recommended in 1960 by the General Conference on
Weights and Measures to simplify and make more logical the many units used in the
scientific and engineering community. Table 1.4 gives the seven base SI units in
terms of which all other units are derived.

Multiples of Units

Quantities expressed in science often range over many orders of magnitude


(many factors of 10). For example, a mole of molecular diatomic nitrogen contains
6.02  1023 N2 molecules and very small particles in the atmosphere may be only
about 1  106 m in diameter. Therefore, prefixes are used that give the number of
times that the basic unit is multiplied. Each prefix has a name and an abbreviation.
Those that are used in this book, or that are most commonly encountered, are given
in Table 1.5.

Metric and English Systems of Measurement

The metric system has long been the standard system for scientific measurement
and is the one most commonly used in this book. It was the first to use multiples
of 10 to designate units that differ by orders of magnitude from a basic unit. The
English system is still employed for many measurements encountered in normal

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Introduction to Chemistry and Green Chemistry 19

Table 1.4. Units of the International System of Units, SI


Physical Quantity Unit
Measured Unit Name Symbol Definition
Base Units
Length metera m Distance traveled by light in a vacuum in
1/299792458 second
Mass kilogram kg Mass of a platinum–iridium block located at the
International Bureau of Weights and Measures
at Sèvres, France
Time second s 9 192 631 770 periods of a specified line in
the microwave spectrum of the cesium-133
isotope
Temperature kelvin K 1/273.16 the temperature interval between
absolute zero and the triple point of water
at 273.16 K (0.01°C)
Amount of mole mol Amount of substance containing as many
substance entities (atoms, molecules) as there are atoms
in exactly 0.012 kilogram of the carbon-12
isotope
Electric current ampere A Based upon current required to generate a
specified force between parallel conductors
Luminous intensity candela cd Based upon power generated by a specified
source of monochromatic light
Examples of Derived Units
Force newton N Force required to impart an acceleration
of 1 m/s2 to a mass of 1 kg
Energy (heat) joule J Work performed by 1 newton acting over
a distance of 1 meter
Pressure pascal Pa Force of 1 newton acting on an area of 1 square
meter
a In the publications of the SI, the British/European spelling “metre” is used.

everyday activities in the U.S., including some environmental engineering measure-


ments. Bathroom scales are still calibrated in pounds, well depths may be given in
feet, and quantities of liquid wastes are frequently expressed as gallons or barrels.
Furthermore, English units of pounds, tons, and gallons are still commonly used in
commerce, even in the chemical industry. Therefore, it is still necessary to have
some familiarity with this system; conversion factors between it and metric units are
given in this book.

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20 Fundamentals of Sustainable Chemical Science

Table 1.5. Prefixes Commonly Used to Designate Multiples of Units


Prefix Basic Unit is Multiplied by Abbreviation
Tera 1 000 000 000 000 (1012) T
Giga 1 000 000 000 (109) G
Mega 1 000 000 (106) M
Kilo 1 000 (10 ) 3 k
Hecto 100 (102) h
Deka 10 (10) da
Deci 0.1 (101) d
Centi 0.01 (102) c
Milli 0.001 (103) m
Micro 0.000 001 (106) μ
Nano 0.000 000 001 (109) n
Pico 0.000 000 000 001 (1012
12) p

1.11. UNITS OF MASS

Mass expresses the degree to which an object resists a change in its state of rest
or motion and is proportional to the amount of matter in the object. Weight is the
gravitational force acting upon an object and is proportional to mass. An object
weighs much less in the gravitational field on the Moon’s surface than on Earth, but
the object’s mass is the same in both places (Figure 1.8). Although mass and weight
are not usually distinguished from each other in everyday activities, it is important
for the science student to be aware of the differences between them.

A cannonball resting on The same cannonball propelled


an astronaut’s foot in an across the spaceship cabin and
orbiting spacecraft would striking the astronaut would be
cause no discomfort painful because of the momen-
because it is weightless tum of its mass in motion.
in outer space.

Figure 1.8. An object retains its mass even in the weightless surroundings of outer space.

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Introduction to Chemistry and Green Chemistry 21

Table 1.6. Metric Units of Mass


Unit of Mass Abbreviation Number of Grams Definition
Megagram or Mg 106 Quantities of industrial chemicals
metric ton (1 Mg  1.102 short tons)
Kilogram kg 103 Body weight and other quantities for which
the pound has been commonly used
(1 kg  2.2046 lb)
Gram g 1 Mass of laboratory chemicals (1 ounce 
28.35 g and 1 lb  453.6 g)
Milligram mg 103 Small quantities of chemicals
Microgram μg 106 Quantities of toxic pollutants

The gram (g), with a mass equal to 1/1000 that of the SI kilogram (see Table 1.4),
is the fundamental unit of mass in the metric system. Although the gram is a conve-
nient unit for many laboratory-scale operations, other units that are multiples of the
gram are often more useful for expressing mass. The names of these are obtained by
affixing the appropriate prefixes from Table 1.5 to “gram.” Global burdens of atmo-
spheric pollutants may be given in units of teragrams, each equal to 1  1012 grams.
Significant quantities of toxic water pollutants may be measured in micrograms
(1  106 grams). Large-scale industrial chemicals are marketed in units of mega-
grams (Mg). This quantity is also known as a metric ton, or tonne, and is somewhat
larger (2205 lb) than the 2000 lb short ton still used in commerce in the United States.
Table 1.6 summarizes some of the more commonly used metric units of mass and
their relationship to some English units.

1.12. UNITS OF LENGTH

Length in the metric system is expressed in units based upon the meter (m)
(see Table 1.4). A meter is 39.37 inches long, slightly longer than a yard (Figure 1.9).
A kilometer (km) is equal to 1000 m and, like the mile, is used to measure relatively
great distances. A centimeter (cm), equal to 0.01 m, is often convenient to designate
lengths such as the dimensions of laboratory instruments. There are 2.540 cm per
inch, and the cm is employed to express lengths that would be given in inches in the
English system. The micrometer (μm) is about as long as a typical bacterial cell.
The micrometer is also used to express wavelengths of infrared radiation by which
Earth re-radiates solar energy back to outer space. (In the past, the micrometer was
sometimes called the “micron,” and abbreviated as simply “,” “ ,” but this term and
abbreviation should no longer be used.) The nanometer (nm), equal to 109 m, is a
convenient unit for the wavelength of visible light, which ranges from 400 to
800 nm. Atoms are even smaller than 1 nm; their dimensions are commonly given

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22 Fundamentals of Sustainable Chemical Science

Figure 1.9. The meter stick is a common tool for measuring length.

in picometers (pm, 101212 m). Table 1.7 lists common metric units of length, some

examples of their use, and some related English units.

1.13. UNITS OF VOLUME

The basic metric unit of volume is the liter (L), which is defined in terms of
metric units of length. As shown in Figure 1.10, a liter is the volume of a decimeter
cubed, that is, 1 L  1 dm3 (a dm is 0.1 m, about 4 inches). A milliliter (mL) is the
same volume as a centimeter cubed (cm3 or cc—although this latter abbreviation
should no longer be used), and a liter is 1000 cm3. A kiloliter, or cubic meter (m3),
is a common unit of measurement for the volume of air. For example, standards for

Table 1.7. Metric Units of Length


Number
Unit of Length Abbreviation of Meters Definition
Kilometer km 103 Distance (1 mile  1.609 km)
Meter m 1 Standard metric unit of length (1 m  1.094 yards)
Centimeter cm 102 Used in place of inches (1 inch  2.54 cm)
Millimeter mm 103 Same order of magnitude as sizes of letters on this page
Micrometer μm 106 Size of typical bacteria
Nanometer nm 109 Measurement of light wavelength
Picometer pm 1012
12 Atomic dimensions

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Introduction to Chemistry and Green Chemistry 23

1 dm

1 dm
1 dm

Figure 1.10. A cube that is 1 decimeter to a side has a volume of 1 liter.

human exposure to toxic substances in the workplace are frequently given in units
of μg/m3. Table 1.8 gives some common metric units of volume. The measurement
of volume is one of the more frequently performed routine laboratory measure-
ments; Figure 1.11 shows some of the more common tools for laboratory volume
measurement of liquids.

1.14. TEMPERATURE, HEAT, AND ENERGY

Temperature Scales

In chemistry, temperatures are usually expressed in metric units of degrees


Celsius (°C), in which water freezes at 0°C and boils at 100°C. The Fahrenheit
scale, still used for some non-scientific temperature measurements in the United
States, defines the freezing temperature of water at 32 degrees Fahrenheit (°F) and
boiling at 212°F, a range of 180°F. Therefore, each span of 100°C is equivalent to
one of 180°F and each °C is equivalent to 1.8°F.

Table 1.8. Metric Units of Volume


Unit of Volumea Abbreviationb Number of Liters Example of Use for Measurement
Kiloliter or cubic kL 103 Volumes of air in air pollution studies
meter
Liter L 1 Basic metric unit of volume (1 liter  1 dm3
 1.057 quarts; 1 cubic foot  28.32 L)
Milliliter mL 103 Equal to 1 cm3. Convenient unit for
laboratory volume measurements
Microliter μL 106 Used to measure very small volumes for
chemical analysis
a In the publications of the SI, the British/European spelling “litre” is used.
b The abbreviation “l” is also frequently used, although it can cause confusion with the number “one.”

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24 Fundamentals of Sustainable Chemical Science

Graduated cylinder Burette for Pipette for Volumetric flask


for approximate accurate quantitative containing a specific,
measurement of measurement of transfer of accurately known
volume varying volumes solution volume

Figure 1.11. Glassware for volume measurement in the laboratory.

The most fundamental temperature scale is the Kelvin or absolute scale, for
which zero is the lowest attainable temperature. A unit of temperature on this scale
is equal to a degree Celsius, but it is called a kelvin
kelvin,, abbreviated K: Kelvin tempera-
tures are designated as K, not °K.
°K. The value of absolute zero on the Kelvin scale is
273.15°C,
273.15°C, so that the Kelvin temperature is always a number 273.15 (usually
rounded to 273) higher than the Celsius temperature. Thus, water boils at 373 K and
freezes at 273 K. The relationships among Kelvin, Celsius, and Fahrenheit tempera-
tures are illustrated in Figure 1.12.

Converting from Fahrenheit to Celsius

With Figure 1.12 in mind, it is easy to convert from one temperature scale to another.
Examples of how this is done are given below.

Example: What is the Celsius temperature equivalent to room temperature


Example:
of 70°F?
Answer:
Answer

Step 11.. Subtract 32°F from 70°F to get the number of degrees Fahrenheit
above freezing. This is done because 0 on the Celsius scale is at the freezing
point of water.

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Introduction to Chemistry and Green Chemistry 25

Celsius Kelvin Fahrenheit

100°C 373 K 212°F Water boils

100° 100° 180°

0°C 273 K 32°F Water freezes

–273°C 0K –459.4°F Absolute zero

Figure 1.12. Comparison of temperature scales.

Step 2.
2. Multiply the number of degrees Fahrenheit above the freezing point
of water obtained above by the number of degrees Celsius per degree
Fahrenheit:
1.00°C  (70°F  32°F)  ______
°C  ______ 1.00°C  38°F  21.1°C (1.14.1)
1.80°F 1.80°F
Factor for conversion Number of °F
from °F to °C above freezing

In working the above example, it is first noted (as is obvious from Figure 1.11) that
the freezing temperature of water, zero on the Celsius scale, corresponds to
32°F on the Fahrenheit scale. So 32°F is subtracted from 70°F to give the number of
degrees Fahrenheit by which the temperature is above the freezing point of water.
The number of degrees Fahrenheit above freezing is converted to degrees Celsius
above the freezing point of water by multiplying by the factor 1.00°C/1.80°F. The
origin of this factor is readily seen by referring to Figure 1.12 and observing that
there are 100°C between the freezing and boiling temperatures of water and 180°F
over the same range. Mathematically, the equation for converting from °F to °C is
simply the following:
1.00°C  (°F  32)
°C  ______ (1.14.2)
1.80°F
Example: What is the Celsius temperature corresponding to the normal
Example:
body temperature of 98.6°F?

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26 Fundamentals of Sustainable Chemical Science

Answer:: From Equation 1.14.2,


Answer
1.00°C  (98.6°F  32°F)  37.0°C
°C  ______ (1.14.3)
1.80°F
Example:: What is the Celsius temperature corresponding to 5°F?
Example 5°F?
Answer:: From Equation 1.14.2,
Answer
1.00°C  ((5°F
°C  ______ 5°F  32°F)  20.6°C
20.6°C (1.14.4)
1.80°F

Converting from Celsius to Fahrenheit

To convert from Celsius to Fahrenheit first requires multiplying the Celsius


temperature by 1.80°F/1.00°C to get the number of Fahrenheit degrees above the
freezing temperature of 32°F, then adding 32°F.

Example:: What is the Fahrenheit temperature equivalent to 10°C?


Example
Answer:
Answer
Step 1. Multiply 10°C by 1.80°F/1.00°C to get the number of degrees
Fahrenheit above the freezing point of water.

Step 2. Since the freezing point of water is 32°F, add 32°F to the result of
Step 1:
1.80°F  °C  32°F  _______
°F  _______ 1.80°F  10°C  32°F  50°F
1.00°C 1.00°C
The formula for converting °C to °F is
1.80°F  °C  32
°F  _______
1.00°C
To convert from °C to K, add 273 to the Celsius temperature. To convert
from K to °C, subtract 273 from K. All of the conversions discussed here can be
deduced without memorizing any equations by remembering that the freezing
point of water is 0°C, 273 K, and 32°F, and the boiling point is 100°C, 373 K,
and 212°F.

Melting Point and Boiling Point

In the preceding discussion, the melting and boiling points of water were both
used in defining temperature scales. These are important thermal properties of any
substance. For the present, melting temperature may be defined as the tempera-
ture at which a substance changes from a solid to a liquid. Boiling temperature is
defined as the temperature at which a substance changes from a liquid to a gas.

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Introduction to Chemistry and Green Chemistry 27

Figure 1.13. Heat energy flow from a hot to a colder object.

More-exacting definitions of these terms, particularly boiling temperature, are given


later in the book.

Heat and Energy

As illustrated in Figure 1.13, when two objects at different temperatures are


placed in contact with each other, the warmer object becomes cooler and the cooler
one warmer until they reach the same temperature. This occurs because of a flow of
energy between the objects. Such a flow is called heat
heat.
The SI unit of heat is the joule (J) (Table 1.4). The kilojoule (1 kJ  1000 J) is
a convenient unit to use to express energy values in laboratory studies. The metric
unit of energy is the calorie (cal), equal to 4.184 J. Throughout the liquid range of
water, essentially 1 calorie of heat energy is required to raise the temperature of 1 g
of water by 1°C. The “calories” that most people hear about are those used to express
energy values of foods and are actually kilocalories (1 kcal  4.184 kJ).

1.15. PRESSURE

Pressure is force per unit area. The SI unit of pressure is the pascal (Pa)
(Table 1.4). The kilopascal (1 kPa  1000 Pa) is often a more convenient unit of
pressure to use than is the pascal.
Like many other quantities, pressure has been plagued with a large number of
different kinds of units. One of the more meaningful and intuitive of these is the atmo-
sphere (atm), and the average pressure exerted by air at sea level is 1 atmosphere. One
atmosphere is equal to 101.3kPa or 14.7 lb/in2. The latter means that an evacuated cube,
1 inch to a side, has a force of 14.70 lb exerted on each side due to atmospheric pressure.
It is also the pressure that will hold up a column of liquid mercury metal 760mm long,
as shown in Figure 1.14. Such a device used to measure atmospheric pressure is called
a barometer
barometer,, and the mercury barometer was the first instrument used to measure
pressures with a high degree of accuracy. Consequently, the practice developed of
expressing pressure in units of millimeters of mercury (mmHg, also called the torr ).
torr).
Pressure is an especially important variable with gases, because the volume of
a quantity of gas at a fixed temperature is inversely proportional to pressure. The
temperature/pressure/volume relationships of gases (Boyle’s law, Charles’ law, and
the general gas law) are discussed in Chapter 2.

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28 Fundamentals of Sustainable Chemical Science

14.70 lb
760 mm

1 in
Atmospheric
pressure
1 in Mercury
reservoir

1 in

Figure 1.14. Average atmospheric pressure at sea level exerts a force of 14.7 pounds on an inch-
square surface. This corresponds to a pressure sufficient to hold up a 760 mm column of mercury.

1.16. UNITS AND THEIR USE IN CALCULATIONS

Most numbers used in chemistry are accompanied by a unit that tells the type of
quantity that the number expresses and the smallest whole portion of that quantity.
For example, “36 liters” denotes that a volume is expressed and the smallest whole
unit of the volume is 1 liter. The same quantity could be expressed as 360 deciliters,
where the number is multiplied by 10 because the unit is only 1/10 as large.
Except in cases where the numbers express relative quantities, such as atomic
masses relative to the mass of carbon-12 or specific gravity, it is essential to include
units with numbers. In addition to correctly identifying the type and magnitude
of the quantity expressed, the units are carried through mathematical operations.
The wrong unit in the answer shows that something has been done wrong in the
calculation and it must be checked.

Unit Conversion Factors

Most chemical calculations involve calculating one type of quantity, given


another, or converting from one unit of measurement to another. For example, in the
chemical reaction

2H2  O2 Æ H2O

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Introduction to Chemistry and Green Chemistry 29

someone might want to calculate the number of grams of H2O produced when 3 g of
H2 react, or they might want to convert the number of grams of H2 to ounces. These
kinds of calculations are carried out with unit conversion factors.
factors. Suppose, for
example, that the mass of a 160 lb person is to be expressed in kilograms; the person
doing the calculation does not know the factor to convert from lb to kg, but does know
that a 551 lb motorcycle has a mass of 250 kg. From this information, the needed unit
conversion factor can be derived and the calculation completed as follows:

Mass of person in kg  160 lb  unit conversion factor (1.16.1)


(problem to be solved)

250 kg  551 lb (known relationship between lb and kg) (1.16.2)

250 kg 551 kg
______  ______  1 (the unit of kg is left on top because it is (1.16.3)
551 1b 551 kg
the unit needed; division is by 551 lb)

Although the concept may be a little difficult to understand, in calculating a unit


conversion factor, the number involved is divided by itself, giving a numerical value
of 1. In making conversions, any quantity multiplied by itself (the unit conversion
factor) is still the same quantity, but just in different units. Dividing 250 kg by 551
lb gives the following conversion factor that can be used to calculate the mass of
the person:

0.454 kg
250 kg ________
______  (1.16.4)
551 1b 1.00 1b

0.454 kg
Mass of person  160 1b  ________  72.6 kg (1.16.5)
1.00 1b

As another example of the use of a unit conversion factor, calculate the number
of liters of gasoline required to fill a 12-gallon fuel tank, given that there are 4 gallons
in a quart and that a volume of 1 liter is equal to that of 1.057 quarts. This problem
can be worked by first converting gallons to quarts, then quarts to liters. The two
unit conversion factors required are the following

1 gal  4 qt (1.16.6)
1 gal 4 qt
_____  _____  1 (conversion from gallons to quarts) (1.16.7)
1 gal 1 gal
1.057 qt  1 L (1.16.8)
1 L  ___
_______ 1 L  1 (conversion from quarts to liters) (1.16.9)
1.057 qt 1L

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30 Fundamentals of Sustainable Chemical Science

Both unit conversion factors are used to calculate the capacity of the tank
in liters:
4 qt 1 L  45.4 L
Tank capacity  12 gal  _____  _______ (1.16.10)
1 gal 1.057 qt

Cancellation of Units

The preceding examples show that units are canceled in mathematical operations,
just as numbers may be. When the same unit appears both above and below the line
in a mathematical operation, the units cancel. An example of such an operation is
shown for lb in the following, in which the unit of lb simply cancels, leaving kg as
the unit remaining:
0.454 kg
160 lb\  ________
1.00 lb\

Calculation of Some Unit Conversion Factors

Several values of units are given that enable conversion between metric and
English units in Table 1.6 (mass), Table 1.7 (length), and Table 1.8 (volume). For
example, Table 1.6 states that a megagram (Mg, metric ton) is equal to 1.102 short
tons (T). By using this equality to give the correct unit conversion factors, it is easy
to calculate the number of metric tons in a given number of short tons of material or
vice versa. To do this, first write the known equality given that a megagram is equal
to 1.102 short tons:

1 Mg  1.102 T (1.16.11)

If the number of Mg is to be calculated given a mass in T, the unit conversion factor


needed is
1 Mg 1.102 T  1
_______  _______ (1.16.12)
1.102 T 1.102 T
leaving Mg on top. Suppose, for example, that the problem is to calculate the mass in Mg of
a 3521 T shipment of industrial soda ash. The calculation involves simply multiplying
the known mass in T times the unit conversion factor required to convert to Mg:
1 Mg
3521 T  _______  3195 Mg (1.16.13)
1.102 T
If the problem had been to calculate the number of T in 789 Mg of copper ore, the
following steps would be followed:
1 Mg
1.102 T  _____
1.102 T  1 Mg _______ 1 (1.16.14)
1 Mg 1 Mg

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